CN108641073B - Trinuclear organic stannous metal catalyst and preparation method and application thereof - Google Patents
Trinuclear organic stannous metal catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 7
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005048 methyldichlorosilane Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 70
- 238000003756 stirring Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000004632 polycaprolactone Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229920001228 polyisocyanate Polymers 0.000 abstract description 2
- 239000005056 polyisocyanate Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 125000004802 cyanophenyl group Chemical group 0.000 abstract 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 30
- 238000002844 melting Methods 0.000 description 22
- 230000008018 melting Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 description 16
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- ZWWKXEXFVYBART-UHFFFAOYSA-N 2,5-diisocyanato-5-methylcyclohexa-1,3-diene Chemical compound O=C=NC1(C)CC=C(N=C=O)C=C1 ZWWKXEXFVYBART-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- -1 amidino compound Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a trinuclear organic stannous metal catalyst and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: under the protection of nitrogen, two molar amounts of n-butyl lithium (LiBu) are usedn) Dehydrogenating aniline of two molar amounts, adding methyl dichlorosilane of one molar amount, adding cyanophenyl of two molar amounts to obtain lithium salt A, and mixing with SnCl of two molar amounts or one molar amount2And reacting to obtain methyl silicon bridged amidino stannous catalyst B or C. The preparation method is simple, the materials are simple and easy to obtain, the price is low, the yield is high, and the purification is easy. The experimental result shows that the catalyst B or C has higher catalytic activity for the polymerization of isocyanate and caprolactone and can be used as a catalyst for preparing polyisocyanate and high molecular weight poly-caprolactone.
Description
Technical Field
The invention relates to an amidino metal catalyst, in particular to a trinuclear organic stannous metal catalyst and a preparation method and application thereof.
Background
Isocyanate polymers and caprolactone polymers are important in everyday life and are widely used in various aspects of production practice. The trimerization product of the isocyanate can enhance the physical properties of the polyurethane, copolymer resin and coating, such as enhancing the thermal resistance, chemical resistance, transparency, impact resistance, and the like. The polymer is a polymer with special properties, and can be widely used for foams, coating materials, adhesives and the like. Polycaprolactone is an important high polymer material, has the outstanding advantage of biodegradable performance, and has great significance in the aspects of green and environmental protection. The polymer has high polymerization property and presents a semi-crystal form, and the crystallinity can reach 45%. It also has good biocompatibility, can be compatible with most synthetic resins, and has high practical value. The polymerization of isocyanates and the polymerization of caprolactone are associated with the development of catalysts.
With the research and study of chemists in various countries, a large number of organic ligands with novel structures are synthesized, and amidino ligands are favored by chemists due to their special structures. The amidino compound has various structures and a simple preparation method, and an N-C-N structure on the amidino can be combined with different substituents to synthesize a plurality of amidino ligands, so that the amidino ligands can be combined with a plurality of metals to generate a plurality of metal complexes, wherein the amidino metal tin compound is also inexhaustible. The organic tin metal compound can effectively catalyze the polymerization of various organic matters such as isonitrile ester ring trimerization (Organometallics,1999,18,4700-4705), caprolactone ring-opening polymerization (Macromolecules,1993,26, 6378-6385; Macromolecules,1988,21,286-293) and the like. There is room for improvement in the conditions and catalytic efficiency for catalyzing the polymerization of isocyanate and caprolactone in the prior related reports. Therefore, the research and development of the novel metal catalyst for catalytically synthesizing the polyisocyanate and the poly-caprolactone has extremely high theoretical significance and application prospect.
Disclosure of Invention
The invention aims to provide a trinuclear organic stannous metal catalyst, a preparation method and application thereof, wherein the catalyst has higher catalytic activity on the polymerization of isocyanate and caprolactone. The catalyst has simple preparation method and easily obtained raw materials.
The invention provides a trinuclear organic stannous metal catalyst, which has the structural formula:
or:
the invention also provides a method for preparing the trinuclear organic stannous metal catalyst, which is characterized by comprising the following steps:
1) preparation of lithium salt: under the protection of nitrogen, reacting 2 moles of aniline and 2 moles of n-butyllithium in an ice-water bath, wherein a solvent is diethyl ether, stirring and reacting to room temperature, cooling to 0 ℃ again after 4 hours, adding 1 mole of methyldichlorosilane, adding 2 moles of benzonitrile, keeping stirring and reacting for 8 hours after the solution is naturally heated to room temperature to obtain an ether solution of lithium salt, filtering, concentrating, and crystallizing to obtain a colorless lithium salt A;
2) preparation of the catalyst: under the protection of nitrogen, SnCl is put into ice-water bath2Adding into tetrahydrofuran solution of lithium salt A, SnCl2The molar ratio of the lithium salt A to the lithium salt A is 2:1 or 1:1, when the solution is naturally heated to room temperature, the solution is kept stirring for reaction for 12 hours, and then dichloromethane is used for extraction, filtration and concentration are carried out to obtain the trinuclear organic stannous metal catalyst B or C.
The catalyst B or C has high catalytic activity for polymerization of isocyanate and caprolactone, and can be used as a catalyst for polymerization of isocyanate and caprolactone.
Compared with the prior art, the invention has the beneficial effects that: 1. the raw materials used for synthesizing the catalyst are simple and easy to obtain, the price is low, the preparation method is simple, and the purification is easy; 2. the catalyst has higher catalytic activity when used for polymerization of isocyanate and caprolactone, and when used for catalyzing p-toluene isocyanate, if a solvent is not added, the catalytic activity is higher, and the reaction is more green and environment-friendly; 3. broadens the field of bridged amidino transition metal isocyanate and caprolactone polymerization catalysts.
Drawings
FIG. 1 is a crystal structure diagram of catalyst B
FIG. 2 is a crystal structure diagram of catalyst C
Detailed Description
The embodiments of the present invention will be further described with reference to the drawings, but these embodiments are not intended to limit the scope of the present invention.
EXAMPLE 1 preparation and characterization of the catalyst
(1) Preparation of lithium salts
Aniline (0.18ml,2mmol) was dissolved in Et under nitrogen2O (30ml) is added under the condition of ice-water bathnBuLi (0.8ml,2.5M,2mmol), stirred to room temperature,after 5h reaction, the solution turned from colorless to light yellow. SiHMeCl is added at 0 DEG C2(0.1ml,1mmol), stirring was continued until room temperature was returned, the reaction stirred overnight and the pale yellow solution turned to a yellow whitish solution. Standing and filtering to obtain a yellow solution. Continuously adding the mixture under the ice-water bath conditionnBuLi (0.8ml,2.5M,2mmol), stirred to room temperature, reacted for 5h, the solution turned to yellowish white turbidity, then benzonitrile (0.2ml,2mmol) was added in an ice water bath, and after returning to room temperature, stirring was continued overnight to turn to yellowish turbidity. Standing, filtering, concentrating the filtrate, and standing overnight without crystal precipitation. And (3) draining to exchange THF, standing for a week at-30 ℃, and slowly precipitating colorless blocky crystals, namely the methylsilicone bridged lithium amidinate, with the yield of 90%.1H-NMR(C6D6300.00MHz, ppm) 7.152-7.120 (m,20H),3.540(s,16H),1.376(s, 3H.) theoretical value of elemental analysis C, 70.55; h, 7.82; n, 7.47%. found: c, 70.15; h, 7.72; and 7.59 percent of N.
(2) Preparation of catalyst B
Under the protection of nitrogen, lithium salt (1.47g,2mmol) is dissolved in THF solution, the solution is yellow, SnCl is added according to the proportion of 2:1 under the condition of ice-water bath2(0.758g,4mmol), left to stand at room temperature and stirred overnight, the solution turned grey turbid, the solvent was drained off and CH was used2Cl2Extracting, standing, filtering to obtain a filtrate which is a yellow-brown solution, concentrating to 15ml, standing at room temperature, and precipitating a colorless blocky crystal after two days, namely a trinuclear organic stannous metal catalyst (hereinafter referred to as catalyst B), wherein the yield is as follows: 88.3 percent.1H-NMR(C6D6,300.00MHz,ppm):7.754–6.934(m,30H),1.015–0.091(m,12H).13C-NMR(C6D675.00MHz) 167.70,132.37,130.93,130.07,129.47,129.04,128.85,127.91 theoretical analysis of elements C, 66.53; h, 5.79; n, 9.46%. found C, 66.49; h, 5.73; n,9.21 percent.
Crystal parameters: chemical formula C40H33N6SiCl3Sn3, Orthorhombic (orthomorphic), space group-P, cell parameter α is 90.00 °, β is 90 °, γ is 90.00 °, V is 9851(3), Z is 8. The crystal structure is shown in figure 1.
Partial bond length: sn 1-N62.253 (8), Sn 2-N22.163 (8), Sn 3-N52.231 (9), Sn3-Cl32.467(4), Si 1-N61.727 (8), Si 1-N41.740 (8), Si 1-N21.743 (8), bond angle (°): N4-Si1-C40108.2(5), N6-Sn 1-N193.8 (3), N6-Si 1-N2106.6 (4), N5-Sn 3-Cl389.7 (3), N2-Si1-C40109.5 (5).
(3) Preparation of catalyst C
Under the protection of nitrogen, THF solution is added into lithium salt compound (1.47g,2mmol), and SnCl is added according to the ratio of 1:1 under the condition of ice-water bath2(0.380g,2mmol), after returning to room temperature and stirring overnight, the solution turned to a pale green turbid solution, the solvent was drained off and CH was used2Cl2Extracting, standing, filtering to obtain a yellow solution, concentrating to 15ml, standing at room temperature, and precipitating a light yellow blocky crystal after one day, namely a trinuclear organic stannous metal catalyst (hereinafter referred to as catalyst C), wherein the yield is as follows: 93.4 percent.1H-NMR(C6D6,300.00MHz,ppm):7.937–6.980(m,55H).13C-NMR(C6D675.00MHz) 153.98,150.19,135.86,130.45, 129.50,128.40,126.64,122.74,121.34 theoretical analytical values of elements C, 52.67; h, 4.11; n, 8.26%. found C, 52.15; h, 4.03; n, 8.09%.
Crystal parameters: chemical formula C173H134N24SiSn6, Monoclinic system (Monoclinic), space group P-1, unit cell parameters α 89.124(1) °, β 69.573(1) °, γ 67.422(1) °, V3599.8 (3), and Z1. The crystal structure is shown in FIG. 2.
Partial bond length: si 1-N41.740 (4), Sn 3-N102.183 (4), Si 2-N101.728 (4), Sn3-N52.530(4), N7-C471.319 (6), bond angle (°): N1-C7-N2120.9 (4), N3-C20-N4118.9 (4), N5-C33-N6120.2 (4), N7-C47-N8119.6 (4), N9-C60-N10119.7 (4), N11-C73-N12120.9 (4).
Example 2
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: under nitrogen protection, catalyst B (0.025g,0.02mmol) was added to a Schlenk flask, diethyl ether (1ml) was added, p-tolylene isocyanate (0.085ml,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, drained, washed three times with diethyl ether (1ml) and drained to give 0.037g of product, a polymer melting point of 265.3 ℃.
Example 3
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: catalyst B (0.025g,0.02mmol) was added to a Schlenk flask under nitrogen, dichloromethane (1ml) was added, then p-toluene isocyanate (0.085ml,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, drained, washed three times with diethyl ether (1ml) and drained to give 0.048g of product, the melting point of the polymer being 265.3 ℃.
Example 4
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: catalyst B (0.025g,0.02mmol) was added to a Schlenk flask under nitrogen, tetrahydrofuran (1ml) was added, p-tolylene isocyanate (0.085ml,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, drained, washed three times with diethyl ether (1ml) and drained to give 0.061g of product having a polymer melting point of 265.3 ℃.
Example 5
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: catalyst B (0.025g,0.02mmol) was added to a Schlenk flask under nitrogen, p-tolylene isocyanate (0.085ml,0.67mmol) was added at a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, pumped dry, washed three times with diethyl ether (1ml) and pumped dry to give 0.067g of product having a polymer melting point of 265.3 ℃.
Example 6
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: under the protection of nitrogen, catalyst C (0.066g,0.02mmol) was added to a Schlenk flask, diethyl ether (1ml) was added, p-tolylene isocyanate (0.085ml,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, drained, washed three times with diethyl ether (1ml) and drained again to give 0.032g of product, the melting point of the polymer being 265.3 ℃.
Example 7
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: under nitrogen protection, catalyst C (0.066g,0.02mmol) was added to a Schlenk flask, followed by dichloromethane (1ml), p-toluene isocyanate (0.085ml,0.67mmol) in a ratio of 3:100 relative to catalyst, stirring at 20 ℃ for 18h, filtration, suction drying, washing three times with diethyl ether (1ml), suction drying again, to give 0.038g of product, melting point of polymer 265.3 ℃.
Example 8
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: under the protection of nitrogen, catalyst C (0.066g,0.02mmol) was added to a Schlenk flask, tetrahydrofuran (1ml) was added, then p-tolylene isocyanate (0.085ml,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, drained, washed three times with diethyl ether (1ml) and drained again to give 0.058g of product, the melting point of the polymer being 265.3 ℃.
Example 9
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing the polymerization of p-toluene isocyanate: catalyst C (0.066g,0.02mmol) was added to a Schlenk flask under nitrogen, p-tolylene isocyanate (0.085ml,0.67mmol) was added at a ratio of 3:100 relative to catalyst C, stirred at 20 ℃ for 18h, filtered, suction dried, washed three times with diethyl ether (1ml) and suction dried to give 0.065g of product having a polymer melting point of 265.3 ℃.
Example 10
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: catalyst B (0.025g,0.02mmol) was added to a Schlenk flask under nitrogen, diethyl ether (1ml) was added, p-chlorophenyl isocyanate (0.095g,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, drained, washed three times with diethyl ether (1ml) and drained to give 0.048g of product, the melting point of the polymer being 268.2 ℃.
Example 11
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: catalyst B (0.025g,0.02mmol) was added to a Schlenk flask, followed by dichloromethane (1ml) and then p-chlorophenyl isocyanate (0.095g,0.67mmol) in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, suction dried, washed three times with diethyl ether (1ml) and suction dried to give 0.057g of product having a melting point of 268.2 ℃.
Example 12
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: catalyst B (0.025g,0.02mmol) was charged to a Schlenk flask, tetrahydrofuran (1ml) was added, p-chlorophenyl isocyanate (0.095g,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, suction dried, washed three times with diethyl ether (1ml) and suction dried to give 0.0627g of product having a melting point of 268.2 ℃.
Example 13
(1) Catalyst B was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: catalyst B (0.025g,0.02mmol) was added to a Schlenk flask followed by p-chlorophenyl isocyanate (0.095g,0.67mmol) in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, suction dried, washed three times with diethyl ether (1ml) and suction dried to give 0.068g of product having a melting point of 268.2 ℃.
Example 14
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: under nitrogen protection, catalyst C (0.066g,0.02mmol) was added to a Schlenk flask, diethyl ether (1ml) was added, p-chlorophenyl isocyanate (0.095g,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, drained, washed three times with diethyl ether (1ml), and drained again to give 0.050g of product, the melting point of the polymer being 268.2 ℃.
Example 15
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: catalyst C (0.066g,0.02mmol) was added to a Schlenk flask, methylene chloride (1ml) was added, then p-chlorophenyl isocyanate (0.095g,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, suction dried, washed three times with diethyl ether (1ml) and suction dried again to give 0.065g of product having a melting point of 268.2 ℃.
Example 16
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: catalyst C (0.066g,0.02mmol) was added to a Schlenk flask, tetrahydrofuran (1ml) was added, p-chlorophenyl isocyanate (0.095g,0.67mmol) was added in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, suction dried, washed three times with diethyl ether (1ml) and suction dried again to give 0.068g of product having a melting point of 268.2 ℃.
Example 17
(1) Catalyst C was prepared as in example 1.
(2) Catalyzing p-chlorophenyl isocyanate polymerization: catalyst C (0.066g,0.02mmol) was added to a Schlenk flask followed by p-chlorophenyl isocyanate (0.095g,0.67mmol) in a ratio of 3:100 relative to catalyst, stirred at 20 ℃ for 18h, filtered, suction dried, washed three times with diethyl ether (1ml) and suction dried again to give 0.085g of product, a polymer having a melting point of 268.2 ℃.
Example 18
(1) Catalyst B was prepared as in example 1.
(2) Catalysis-caprolactone polymerization in nitrogen atmosphere, adding catalyst B (0.025g,0.02mmol) into a Schlenk bottle, injecting a certain amount of toluene (1ml) by a syringe, then adding caprolactone (0.21ml,2mmol) with the ratio of catalyst B to caprolactone being 1:100, stirring at 110 ℃ until the reaction is stirred to be viscous, adding two drops of acetic acid, then continuing to stir for 20min, adding 50ml of methanol, filtering, pumping to dryness to obtain a product of 0.139g, wherein the weight average molecular weight of the obtained polymer is 2.543 × 104g·mol-1The molecular weight distribution was 1.82 and the melting point of the polymer was 59.8 ℃.
Example 19
(1) Catalyst B was prepared as in example 1.
(2) Catalysis-caprolactone polymerization, catalyst B (0.025g,0.02mmol) is added into a Schlenk bottle, a certain amount of toluene (1ml) is injected by a syringe, caprolactone (0.43ml,4mmol) is added according to the ratio of catalyst B to caprolactone being 1:200, stirring is carried out at 110 ℃ until the reaction is stirred to be viscous, two drops of acetic acid are added, stirring is continued for 20min, 50ml of methanol is added, filtering and pumping-out are carried out, and the obtained polymer has the weight average molecular weight of 2.410 × 10.301 g, and the obtained polymer has the weight average molecular weight of 89104g·mol-1The molecular weight distribution was 1.91 and the melting point of the polymer was 59.8 ℃.
Example 20
(1) Catalyst B was prepared as in example 1.
(2) Catalysis-caprolactone polymerization catalyst B (0.025g,0.02mmol) was added to a Schlenk flask, a certain amount of toluene (1ml) was injected with a syringe, caprolactone (0.64ml,6mmol) was added at a ratio of catalyst B to caprolactone of 1:300, stirring was carried out at 110 ℃ until the reaction was viscous, two drops of acetic acid were added, stirring was continued for 20min and 50ml of methanol was added, filtering and suction drying were carried out to obtain 0.499g of a product, the weight average molecular weight of the resulting polymer was 2.239 × 10 g4g·mol-1The molecular weight distribution was 1.79 and the melting point of the polymer was 59.8 ℃.
Example 21
(1) Catalyst C was prepared as in example 1.
(2) Catalysis-caprolactone polymerization catalyst C (0.066g,0.02mmol) was added to a Schlenk flask, a certain amount of toluene (1ml) was injected with a syringe, caprolactone (0.21ml,2mmol) was added at a ratio of catalyst C to caprolactone of 1:100, stirring was carried out at 110 ℃ until the reaction was viscous, two drops of acetic acid were added, stirring was continued for 20min and 50ml of methanol was added, filtering and suction drying were carried out to give 0.153g of the product, the weight average molecular weight of the resulting polymer was 2.018 × 104g·mol-1The molecular weight distribution was 1.93 and the melting point of the polymer was 59.8 ℃.
Example 22
(1) Catalyst C was prepared as in example 1.
(2) Catalysis-caprolactone polymerization, catalyst C (0.066g,0.02mmol) is added into a Schlenk bottle, a certain amount of toluene (1ml) is injected by a syringe, caprolactone (0.43ml,4mmol) is added according to the ratio of catalyst C to caprolactone being 1:200, stirring is carried out at 110 ℃ until the reaction is stirred to be viscous, two drops of acetic acid are added, stirring is continued for 20min, 50ml of methanol is added, filtering and pumping-out are carried out, and the product is obtained, wherein the weight average molecular weight of the obtained polymer is 2.108 × 10 g4g·mol-1The molecular weight distribution was 1.76 and the melting point of the polymer was 59.8 ℃.
Example 23
(1) Catalyst C was prepared as in example 1.
(2) Catalysis-caprolactone polymerization, catalyst C (0.066g,0.02mmol) is added into a Schlenk bottle, a certain amount of toluene (1ml) is injected by a syringe, caprolactone (0.64ml,6mmol) is added according to the ratio of catalyst C to caprolactone being 1:300, stirring is carried out at 110 ℃ until the reaction is stirred to be viscous, two drops of acetic acid are added, stirring is continued for 20min, 50ml of methanol is added, filtering and pumping-out are carried out, and the weight average molecular weight of the obtained polymer is 2.242 × 10 g, so that the obtained polymer is 0.547g4g·mol-1The molecular weight distribution was 1.88, and the melting point of the polymer was 59.8 ℃.
Claims (4)
1. A trinuclear organic stannous metal catalyst characterized by the following structural formula:
or:
2. a process for preparing the catalyst of claim 1, comprising the steps of:
1) preparation of lithium salt: under the protection of nitrogen, reacting 2 moles of aniline and 2 moles of n-butyllithium in an ice-water bath, wherein a solvent is diethyl ether, stirring and reacting to room temperature, cooling to 0 ℃ again after 4 hours, adding 1 mole of methyldichlorosilane, adding 2 moles of benzonitrile, keeping stirring and reacting for 8 hours after the solution is naturally heated to room temperature to obtain an ether solution of lithium salt, filtering, concentrating, and crystallizing to obtain a colorless lithium salt A;
2) preparation of the catalyst: under the protection of nitrogen, SnCl is put into ice-water bath2Adding into tetrahydrofuran solution of lithium salt A, SnCl2The molar ratio of the lithium salt A to the lithium salt A is 2:1 or 1:1, when the solution is naturally heated to room temperature, the solution is kept stirring for reaction for 12 hours, and then dichloromethane is used for extraction, filtration and concentration are carried out to obtain the trinuclear organic stannous metal catalyst B or C.
3. Use of the trinuclear organic stannous metal catalyst of claim 1 in isocyanate polymerization.
4. Use of the trinuclear organic stannous metal catalyst of claim 1 in caprolactone polymerization.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1764379A1 (en) * | 2005-09-19 | 2007-03-21 | DSM IP Assets B.V. | Polymerization catalyst comprising an amidine ligand |
| CN101500989A (en) * | 2006-06-28 | 2009-08-05 | 哈佛学院院长等 | Metal(IV) tetra-amidinate compounds and their use in vapor deposition |
| WO2011156699A1 (en) * | 2010-06-11 | 2011-12-15 | Air Products And Chemicals, Inc. | Complexes of imidazole ligands |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1764379A1 (en) * | 2005-09-19 | 2007-03-21 | DSM IP Assets B.V. | Polymerization catalyst comprising an amidine ligand |
| CN101500989A (en) * | 2006-06-28 | 2009-08-05 | 哈佛学院院长等 | Metal(IV) tetra-amidinate compounds and their use in vapor deposition |
| WO2011156699A1 (en) * | 2010-06-11 | 2011-12-15 | Air Products And Chemicals, Inc. | Complexes of imidazole ligands |
Non-Patent Citations (1)
| Title |
|---|
| "均配亚锡脒基化合物的合成及其对对甲苯异氰酸酯和ε-己内酯的催化";贺宏竹等;《山西大学学报（自然科学版）》;20180105;第41卷(第3期);第 * |
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